EP0158592A1 - Aluminosilikate optische Gläser - Google Patents

Aluminosilikate optische Gläser Download PDF

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Publication number
EP0158592A1
EP0158592A1 EP85810088A EP85810088A EP0158592A1 EP 0158592 A1 EP0158592 A1 EP 0158592A1 EP 85810088 A EP85810088 A EP 85810088A EP 85810088 A EP85810088 A EP 85810088A EP 0158592 A1 EP0158592 A1 EP 0158592A1
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EP
European Patent Office
Prior art keywords
glass
exchange
metals
glasses
hrs
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP85810088A
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English (en)
French (fr)
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EP0158592B1 (de
Inventor
Carlos Gonzales-Oliver
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Battelle Memorial Institute Inc
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Battelle Memorial Institute Inc
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Filing date
Publication date
Application filed by Battelle Memorial Institute Inc filed Critical Battelle Memorial Institute Inc
Priority to AT85810088T priority Critical patent/ATE40098T1/de
Publication of EP0158592A1 publication Critical patent/EP0158592A1/de
Application granted granted Critical
Publication of EP0158592B1 publication Critical patent/EP0158592B1/de
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00—Fibre or filament compositions
    • C03C13/04—Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045—Silica-containing oxide glass compositions
    • C03C13/046—Multicomponent glass compositions
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C21/00—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface
    • C03C21/001—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions
    • C03C21/005—Treatment of glass, not in the form of fibres or filaments, by diffusing ions or metals in the surface in liquid phase, e.g. molten salts, solutions to introduce in the glass such metals or metallic ions as Ag, Cu
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S65/00—Glass manufacturing
    • Y10S65/901—Liquid phase reaction process

Definitions

  • the subject of the present invention is aluminosilicate optical glasses containing at least one oxide of a monovalent modifier metal chosen from Tl and Ag.
  • These glasses which can additionally contain cesium, are characterized by their composition which comprises, in moles %, 60 to 95 of silica, at least 2 of alumina and at least 2 of an oxide or oxides of the abovementioned metals.
  • the molar proportions of Al 2 O 3 and of modifying metal oxides are greater than 3, the proportion of SiO 2 being less than 94%.
  • Such glasses are particularly useful in the field of waveguides for optical transmissions because they have the ability, under certain conditions, to exchange the cation of the monovalent metal with a foreign cation, this operation resulting in a change, in the glass thus treated, of the refractive index.
  • waveguides is meant, for example, both the microlenses covering the optical fibers and serving to inject light signals therein as well as the fibers themselves.
  • a waveguide having such properties one generally starts from a glass of homogeneous index to which an appropriate shape is given (bar, for example, which can later be molded in the form of a microlens or stretched in the form of fiber) and the composition of which comprises one or more metals capable of diffusing towards the outside and of being gradually replaced, by another metal whose presence results in a refractive index different from that of the base glass.
  • an appropriate shape bar, for example, which can later be molded in the form of a microlens or stretched in the form of fiber
  • the composition of which comprises one or more metals capable of diffusing towards the outside and of being gradually replaced, by another metal whose presence results in a refractive index different from that of the base glass.
  • this quotient being relatively low for certain metals whose influence on the refractive index is weak, for example alkali and alkaline earth metals (0.06 for Li; 0.56 for K; 0.2 for Mg) but significantly higher for metals such as cesium (C, 744), thallium (1.572) and silver, the influence of the oxides of these metals on the refractive index being much more significant.
  • Document FR-A-2.175.934 describes the manufacture of stretchable glass preforms with variable refractive index by ion exchange in a bath of molten salt.
  • glasses used as starting materials for such an exchange mention is made of borosilicate glasses containing cesium, thallium and, optionally, alumina.
  • the glasses of the invention do not contain boron oxide, which gives them increased stability in applications relating to telecommunications.
  • these preforms can be molded or stretched well into optical fibers by the usual means, the qua lity thereof being excellent due to the low tendency to microcracking of the glasses of the invention.
  • the existence in the present glasses of high proportions of both alumina and diffusable metal (s) leads to an open structure promoting a very rapid cation exchange and therefore saving of processing energy.
  • the glasses of the invention contain from 2 to 20 mole% of Al 2 O 3 and from 2 to 20 mole% of oxides of Tl, Cs or Ag, silver and thallium being able to intervene individually and the cesium in mixture with one, the other or the 2 preceding metals.
  • These limits are not, however, mandatory and may be exceeded in certain special cases.
  • the molar proportions of Al 2 O 3 and of the modifying metals are not necessarily equal, the excess of one being able to compensate for a lack of the other.
  • This gel is then dried and, by heating to a relatively low temperature (900 - 1200 ° C) it is subjected to a sort of sintering or densification into a homogeneous and exceptionally pure glass.
  • a relatively low temperature 900 - 1200 ° C
  • This technique is particularly suitable for the glasses of the invention (relatively low densification temperatures) because the oxides of Tl, Cs and Ag are very volatile at the temperatures normally applied during the implementation of the usual melting processes (1500 ° C or higher) and, in such cases, the losses in such oxides would be considerable and incompatible with economical manufacture.
  • the sol-gel process offers the major advantage of allowing additional doping in thallium, cesium or silver by intervening at the stages preceding the final densification where the structure passes from the porous and translucent state to that of glass. perfectly transparent. Indeed, at the preliminary stages where the material resulting from the gelling of the alkyd solution is in the form of a rigid gel more or less condensed (depending on the drying and densification temperatures to which it has already been subjected) porosity allows it to absorb in its interstitial voids an additional dose of doping metals (for example provided by a bath of molten salts in which the porous preform is soaked for a given time).
  • doping metals for example provided by a bath of molten salts in which the porous preform is soaked for a given time.
  • a pressure sintering mold was filled with glass particles ("crumbs") resulting from the breakage of a sample subjected to treatment II above and was subjected to a pressing of 4 t / cm2 at 1200 ° C. for 60 min. Preforms similar to those of Example 2 were thus obtained, the temperature used for sintering, significantly lower than the normal glass melting temperature, being insufficient to cause the volatilization of a significant amount of oxy of cesium and thallium oxide.
  • the glasses were prepared in the form of stretchable preforms for optical fibers.
  • Sample 3 without alumina, was prepared for control purposes; its behavior, during the cation exchange reactions described below, was different from that of the glasses of the invention.
  • the attached drawing schematically represents the variation radia the height of the main peaks K and Cs when the same analysis is carried out by scanning a straight section of the glass sample, this scanning being carried out in a direction connecting the periphery p to the center c of this section .
  • a similar variation is observed with regard to thallium.
  • a corresponding measurement of the refractive index, which is a function of the simultaneous presence of Cs, Tl and K, has shown that the variation of the latter follows a curve which is clearly approaching the parabola sought.
  • the glasses obtained in tests 1, 2 and 4-6 of Example 5 By subjecting the glasses obtained in tests 1, 2 and 4-6 of Example 5 to the cation exchange described above, similar results are obtained, the glasses containing silver having a particularly satisfactory behavior in as regards the variation of the refractive index gradient which, depending on the degree of exchange, that is to say the treatment time which can be continued up to 10-20 hours, can reach 15% between the center and the periphery of the bar.
  • the cation exchange treatment was also carried out in a molten metal bath of glass sample prepared according to the techniques described above, but before final densification.
  • samples of varying degrees of porosity as obtained after the heating stages 1, 2 and 3 described in Example 1 were subjected to such treatment.
  • a final densification of the glass was carried out as corresponding to the heating operation 4. of Example 1.
  • the variation profile of the refractive index between the periphery and the center of the bar may deviate from the ideal curve, if the treatment is too prolonged or if the temperature is too high.
  • the development of the exact conditions to obtain a determined profile curve is easily carried out from case to case by routine tests.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Glass Compositions (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Surface Treatment Of Glass (AREA)
  • Optical Fibers, Optical Fiber Cores, And Optical Fiber Bundles (AREA)
EP85810088A 1984-03-07 1985-03-04 Aluminosilikate optische Gläser Expired EP0158592B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85810088T ATE40098T1 (de) 1984-03-07 1985-03-04 Aluminosilikate optische glaeser.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1131/84A CH657118A5 (fr) 1984-03-07 1984-03-07 Verres optiques aluminosilicates.
CH1131/84 1984-03-07

Publications (2)

Publication Number Publication Date
EP0158592A1 true EP0158592A1 (de) 1985-10-16
EP0158592B1 EP0158592B1 (de) 1989-01-18

Family

ID=4203221

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85810088A Expired EP0158592B1 (de) 1984-03-07 1985-03-04 Aluminosilikate optische Gläser

Country Status (7)

Country Link
US (2) US4731348A (de)
EP (1) EP0158592B1 (de)
JP (1) JPS61501320A (de)
AT (1) ATE40098T1 (de)
CH (1) CH657118A5 (de)
DE (1) DE3567627D1 (de)
WO (1) WO1985003928A1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0250635A1 (de) * 1985-03-29 1988-01-07 Hoya Corporation Verfahren zur Herstellung einer Linse mit Brechwertgradient

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH657118A5 (fr) * 1984-03-07 1986-08-15 Battelle Memorial Institute Verres optiques aluminosilicates.
US4797376A (en) * 1987-06-09 1989-01-10 University Of Rochester Sol-gel method for making gradient-index glass
US5071674A (en) * 1989-11-30 1991-12-10 The University Of Florida Method for producing large silica sol-gels doped with inorganic and organic compounds
US5068208A (en) * 1991-04-05 1991-11-26 The University Of Rochester Sol-gel method for making gradient index optical elements
US5261022A (en) * 1991-10-21 1993-11-09 Photonic Integration Research, Inc. Optical waveguide of silica glass film on ceramic substrate
US5476881A (en) * 1993-02-15 1995-12-19 Suh; Kang I. Antimicrobial composition for manufacturing nipples
US5613995A (en) * 1993-04-23 1997-03-25 Lucent Technologies Inc. Method for making planar optical waveguides
US6136736A (en) * 1993-06-01 2000-10-24 General Electric Company Doped silica glass
US5631522A (en) * 1995-05-09 1997-05-20 General Electric Company Low sodium permeability glass
US6128926A (en) * 1999-03-15 2000-10-10 Dicon Fiberoptics, Inc. Graded index lens for fiber optic applications and technique of fabrication
ITUA20164808A1 (it) * 2016-06-30 2017-12-30 Bormioli Pharma S R L Metodo e apparato di rilevamento di particelle metalliche presenti in una parete di un contenitore in vetro.

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2127010A (en) * 1982-09-14 1984-04-04 Nippon Sheet Glass Co Ltd Thallium-containing optical glass composition

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1279464A (en) * 1968-10-03 1972-06-28 Nippon Selfoc Co Ltd Production of light conducting glass fibres
GB1413891A (en) * 1972-03-10 1975-11-12 Nippon Selfoc Co Ltd Optical glass bodies
US3802761A (en) * 1972-12-07 1974-04-09 Us Navy Optical waveguide edge coupler using graded index profile
US3888648A (en) * 1972-12-07 1975-06-10 Us Navy Method for forming an optical wave guide coupler
GB2086877B (en) * 1980-09-17 1985-01-23 Sumitomo Electric Industries Producing graded index optical glass articles from silica gel bodies
JPS57188431A (en) * 1981-05-12 1982-11-19 Nippon Sheet Glass Co Ltd Optical glass containing thallium
CH657118A5 (fr) * 1984-03-07 1986-08-15 Battelle Memorial Institute Verres optiques aluminosilicates.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2127010A (en) * 1982-09-14 1984-04-04 Nippon Sheet Glass Co Ltd Thallium-containing optical glass composition

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 99, no. 14, 3 octobre 1983, page 257, no. 109518, Columbus, Ohio, US; R. JHUN et al.: "Preparation of aluminum silicate (Al7O3.2SiO2) glass by the sol-gel process" & YO OP HOE CHI, 1983, 20(1), 3-12 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0250635A1 (de) * 1985-03-29 1988-01-07 Hoya Corporation Verfahren zur Herstellung einer Linse mit Brechwertgradient

Also Published As

Publication number Publication date
ATE40098T1 (de) 1989-02-15
JPS61501320A (ja) 1986-07-03
WO1985003928A1 (fr) 1985-09-12
US4851023A (en) 1989-07-25
EP0158592B1 (de) 1989-01-18
US4731348A (en) 1988-03-15
CH657118A5 (fr) 1986-08-15
DE3567627D1 (en) 1989-02-23

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